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Publication numberUS4116759 A
Publication typeGrant
Application numberUS 05/719,139
Publication dateSep 26, 1978
Filing dateAug 31, 1976
Priority dateSep 2, 1975
Also published asCA1087355A1
Publication number05719139, 719139, US 4116759 A, US 4116759A, US-A-4116759, US4116759 A, US4116759A
InventorsJan Janson
Original AssigneeJan Janson
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Preparation of liquor for delignification or alkali treatment by autocaustization, and the preparation of pulp with this liquor
US 4116759 A
Abstract
A method for the regeneration of pulping or bleaching chemicals from spent liquor containing salts of polybasic organic acids. The liquor is evaporated and then burned so that organic matter will be discharged as carbon dioxide and water, and a carbonate residue is formed. Carbon dioxide is expelled from the carbonate with an acid by autocaustization to regenerate the cooking chemicals.
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Claims(8)
I claim:
1. A method for the alkali pulping of ligno-cellulose materials, comprising the steps of cooking the ligno-cellulose material in an alkaline aqueous cooking liquor containing as an active ingredient at least one alkaline salt of a polybasic inorganic acid selected from the group consisting of NaH2 BO3 and Na2 HBO3, combusting the residual cooking liquor to obtain an alkaline inorganic substance, and dissolving said inorganic substance in water to provide the same alkaline salt as used in the cooking step.
2. The method of claim 1, wherein the polybasic acid is boric acid and the borate salt is used in a concentration of 0.1-2.0 mol B/1 and so that during the pulping process 0.2-2.0 mols of hydroxyl ions per mol of boron are liberated through hydrolysis of the salt.
3. The method of claim 1, wherein the liquor is evaporated prior to combusting.
4. The method of claim 1 wherein the acid is boric acid, and the borate in said residual liquor has a molar ratio Na:B of 1-2 (excluding Na present as Na2 S) and is combusted at a temperature of 200 C. to 1500 C.
5. A method for the alkaline bleaching of pulp derived from ligno-cellulose materials, the steps comprising bleaching the pulp in the presence of oxygen in an aqueous alkaline liquor containing as an active ingredient at least one alkaline salt of a polybasic inorganic acid selected from the group consisting of Na2 HBO3 and NaH2 BO3, combusting the residual liquor to obtain an alkaline inorganic substance, and dissolving the inorganic substance in water to form the same alkaline salt used in the bleaching step.
6. The method of claim 5, wherein the alkaline salt is used in a concentration of 0.1 to 2.0 mols of boron/1 so that during the bleaching process 0.2 to 2.0 mols of hydroxyl ions per mol of boron are liberated through hydrolysis of the salt.
7. The method of claim 5, wherein the liquor is evaporated prior to combustion.
8. The method of claim 5, wherein the alkaline salt in said residual liquor has a molar ratio of Na:B of 1-2 (excluding Na present as Na2 S) and is combusted at a temperature at 200 C. to 1500 C.
Description
BACKGROUND OF THE INVENTION

When alkaline spent pulping liquors are burnt to yield chemicals and heat, one of the main products is sodium carbonate. In the case of black liquor from kraft cooks, sodium sulfide will also be formed. The product is dissolved in water into so-called green liquor after the passage through the recovery furnace. As a rule, the carbonate is usually not sufficiently alkaline to pulp wood or similar fibrous material to an adequate degree. The carbonate is consequently transformed into hydroxide. This process is called caustisation, and is conducted with the aid of a metal hydroxide solution, of which the corresponding carbonate has a low solubility in water. In practice, calcium hydroxide is used for the caustisation. In addition to soluble sodium hydroxide, insoluble calcium carbonate is also formed (lime sludge), which is usually separated, heated (lime sludge reburning), until it has been transformed into calcium oxide and is then dissolved into new calcium hydroxide. Caustisation requires both equipment and time, and if it could be avoided this would mean a considerable saving for a pulp mill.

SUMMARY OF THE INVENTION

The present invention is intended to eliminate the caustisation by addition of a chemical and separation of a byproduct, as used in the past. This can be achieved by the use of chemicals other than the conventional ones by alkaline pulping processes. Since alkali is required also for the bleaching of pulp, conventional bleaching alkali can be substituted by chemicals, which can be regenerated according to the present invention.

Another advantage in cooking and bleaching with these chemicals is, that a more even pH value is obtained, and thereforeless carbohydrate degradation.

In addition, the chemicals can be used for alkali treatment of pulp that has already been made, for example, in connection with viscose preparation. Also such liquor can be prepared according to the invention.

DESCRIPTION OF THE DRAWINGS

The drawings illustrate the best mode presently contemplated of carrying out the invention.

In the drawings:

FIG. 1 is a graphic illustration of the completeness of caustisation of a given borate-carbonate ratio at different temperatures;

FIG. 2 is a graphic illustration showing the completeness of caustisation of various molar ratios of borates and phosphates; and

FIG. 3 is a graphic illustration showing the completeness of caustisation of various molar ratios of phosphates at different temperatures.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The caustisation procedure according to the invention will hereinafter be called autocaustisation. It is applicable if use is made of certain salts of polyprotic inorganic acids, such as boric or orthophosphoric acid, as pulping chemicals (or bleaching chemicals -- generally: delignification chemicals). After such use, the liquor is evaporated and burnt, whereafter in the main its content of organic matter will have been transformed into carbon dioxide and water, whereby part of the carbon dioxide will be bound in the form of carbonate to the non-volatile residue ("ash" or "melt", depending upon the temperature). At a sufficiently high temperature, the carbon dioxide is expelled from the carbonate without the addition of a separate chemical. In principle. the following three stages can be noticed for the alkali, where the Na2 HBO3 and alkali-consuming organic matter in the cook, such as lignin, by LignOH.

1. cooking or bleaching (delignification):

Na2 HBO3 LignOH ⃡ LignONa+NaH2 BO3 

2. combustion:

2 LignONa+x.O2 →Na2 CO3 +y.CO2 +z.H2 O

3. autocaustisation:

2NaH2 BO3 +Na2 CO3 →2Na2 HBO3 +CO2 +H2 O

the principle of autocaustisation is based on the fact that one can expel the carbon dioxide from carbonate with an acid, H2 BO3, which is weaker than carbon dioxide, provided one or several reaction products (in this case CO2 and H2 O) are removed from the system. The equilibrium in reaction 3 may thus be inclined to the left, but since CO2 and H2 O are allowed to leave continuously, the product Na2 HBO3 can be obtained in a theoretical yield. However, it should be noted that the cooking chemical in both its uncausticised and its causticised form (NaH2 BO3 and Na2 HBO3, resp) should be non-volatile; it normally is so if it is a sodium salt. If the causticised product Na2 HBO3 is sufficiently alkaline, it is usable as a delignification chemical. This is the case with secondary sodium borate, Na2 HBO3, which has been shown approximately to correspond equimolarly to NaOH as effective alkali during alkaline pulping.

The salt Na2 HBO3 does not exist as such in a dry state, but dehydrated, viz. according to the formula:

2 Na2 HBO3 ⃡Na4 B2 O5 +H2 O

however, by redissolution in water the salt is hydrolysed back to orthoborate. In the subsequent text, Na2 HBO3, and generally Nam+1 Hn-1 A, are also allowed to represent such salts of corresponding polynuclear ions.

The borate salt is used in a concentration of 0.1 to 2.0 mols of boron/liter so that during the pulping or bleaching process 0.2 to 2.0 mols of hydroxyl ions per mol of boron are liberated through hydrolysis of the salt.

The borate in the residual liquor has a molar ratio of Na:B of 1 - 2 (excluding Na present as Na2 S) and is combusted at a temperature of 200 l C. to 1500 C., with dissolution of the residue in water following.

The conditions needed for autocaustisation depend upon the nature of the chemical concerned. As is shown in FIG. 1, one can achieve with a mixture of 2 mol NaH2 BO3 and 1 mol Na2 CO3 (when thus the total molar ratio F = Na:B is equal to 2.0), by heating at 875 C. for 3 h there is attainable a degree of caustisation of 80% (20% CO2 of original amount remaining). Caustisation experiments with the same borate-carbonate mixture have been performed within the temperature interval 725-875 C. (see FIG. 1) for times between 0 and 3 h 30 min. It appeared that the decomposition of the carbonate approximately followed first order kinetics, and that the reaction constant k (is s-1) could be calculated by means of the equation:

lnk = 2.67 - (13350/T)

where T is the absolute temperature in K (Kelvin). The energy of activation was 111 kJ/mol, which may for example mean, that the reaction speed is doubled if the temperature is increased from 875 to 947 C.; If the molar ratio F varies, it is obvious that it is easy to causticise if F≦2, but not if F>2 (see FIG. 2). This is also to be expected, since if F>2, the mixture will consist of NaH2 BO3 and Na2 CO3, and carbon dioxide can be expected to be expelled by the ion H2 BO3 (whereby HBO3 2- will be formed), but not by the ion HBO3 2-, which is not a sufficiently strong acid.

Analogous experiments with phosphate have shown, that it is possible to perform the following autocaustisation:

2 Na2 HPO4 +Na2 CO3 →2 Na3 PO4 +CO2 +H2 O

as is shown in FIG. 3, after about 40 min at 525 C. 80% of the carbon dioxide has been expelled, and at 625-725 C. as much as 90%. If the molar ratio G = Na:P exceeds 3, caustisation will be incomplete (see FIG. 2); if G≧4, no caustisation will occur. For example, if G = 3.5, the mixture will be causticised half-way (FIG. 3):

na3 PO4 +Na2 HPO4 +Na2 CO3 →2 Na3 PO4 +1/2Na2 CO3 +1/2CO2 +1/2H2 O

thus, for borate - and phosphate liquor it is essential to keep F = Na/B≦2 and G=Na:P≦3, respectively, to ensure complete caustisation. Salts of other amphoteric electrolytes silicates and aluminates, such as might also be used analogously.

Experiments have also been made with organic substance present during the heating of borate- and phosphate salts in the presence of air, to simulate the burning and caustisation of real spent liquors. Thus, Na2 HBO3 and Na3 PO4, respectively, have been mixed with vanilline and glucose (and some water) and heated in a laboratory oven. The caustisation then proceeded a little more slowly than when pure carbonate was present instead of the organic compounds, see Fig. 1.

Examples are given below from experiments with real pulping spent liquors (birch liquors, corresponding to pulp yields of 65-79%):

__________________________________________________________________________Composition  Theoretical amount              Found amount after                           Degree                                Mainof original  after combustion of 1 1              combustion and heating                           of caus-                                productcooking  spent liquor, mmol              of 1 1 spent liquor, mmol                           tisation                                after dis-liquor Na B  P  CO2              Na B  P  CO2                           %    solution__________________________________________________________________________NaOH   1000     -- -- 500               881                 -- -- 283 36   Na2 CO3Na2 HBO3  1740     870        -- 435              1686                 949                    -- 23  95   Na2 HBO3NaBO3   550     550        --  0  523                 518                    --  3  --   NaH2 BO3Na3 PO4  3750     -- 1250           625              3986                 -- 1340                       76  89   Na3 PO4__________________________________________________________________________

The degree of caustisation refers to that part of the carbonate formed during combustion which has expelled its CO2 during heating.

It is thus obvious that one can burn and regenerate borate- and phosphate spent liquors by heating (autocaustisation) in such a way as to give liquors which are re-usable as alkali for the preparation of pulps.

Both kraft and "soda" cooking can be done with borate or phosphate instead of hydroxide as alkali, as can bleaching, for instance oxygen bleaching.

Examples of birch kraft cooks at a liquor - to - wood ratio of 3.6, and to a H-factor of 981:

______________________________________           Total                  Degree           yield   Screen-        ofCooking chemicals, mol/l           % of    ings %   Lignin                                  deligni-Na2 S  NaOH     Na2 HBO3                   wood  of wood                                %     fication______________________________________0.20  0.98    --        52.4  0.1     3.8  0.900.22  --      1.14      52.4  0.2     3.1  0.92______________________________________

An example is given below of "soda" cooks of birch (liquor - to - wood ratio 4.0):

______________________________________                                  Degree                    Total    Lig- ofCooking chemicals, mol/l            H       yield %  nin  deligni-NaOH  Na2 HBO3           Na3 PO4                    factor                          of wood                                 %    fication______________________________________--    0.61      --       533   69.4   21.2 0.290.80  --        --       482   68.1   20.1 0.34--    --        1.50     482   69.9   21.0 0.29______________________________________

From a number of kraft and alkali cooks of birch it has been found, that 1 mol Na2 HBO3 corresponds to 1.2 mol NaOH, and that 1 mol Na3 PO4 corresponds to about 0.5-0.6 mol NaOH during cooking.

The following oxygen bleaching experiments may be presented as examples of the use of weakly-alkaline NaH2 BO3. The starting material was birch alkali pulp, cooked to the yield 67.4%, and with lignin content 21.7%. During the bleaching, the pulp consistency was 10%, the oxygen pressure 8 bar, the maximum temperature 120 C. and the time at 120 C. 45 min.

__________________________________________________________________________        Total    Degree   Bright-        yield, % of  Viscosity                          nessAlkali, mol/l     Final        after             Lignin                 deligni-                     SCAN SCANNaOH    NaH2 BO3     pH bleaching             %   fication                     dm3 /kg                          %__________________________________________________________________________0.29    --    10.9        54.9 11.2                 0.70                     690  33.0--  0.60   9.9        57.0 11.1                 0.70                     740  32.1__________________________________________________________________________

In this case the advantage with weak alkali was that at a certain lignin content the yield was about 2 abs. % higher.

According to the invention, it is thus possible to use alkaline borate, such as Na2 HBO3, instead of hydroxide during pulping, and it is also possible, after the organic material in the spent liquor has been burnt into carbonate, to causticise the remainder by heating, so as to obtain new alkaline liquor suitable for use in pulping. Alkali losses during the pulping cycle may be covered by borax and soda. Analogously, bleaching alkali may be prepared, and also analogously, other inorganic chemicals may be used.

Various modes of carrying out the invention are contemplated as being within the scope of the following claims particularly pointing out and distinctly claiming the subject matter which is regarded as the invention.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4248662 *Jan 22, 1979Feb 3, 1981The Black Clawson CompanyDelignification of wood using sodium tetraborate
US6294048Jan 28, 1999Sep 25, 2001U.S. Borax Inc.Partially autocausticizing a sodium carbonate-containing smelt by reaction with borate; dissolving borate-containing partially autocausticized smelt in aqueous solution; introducing lime to regenerate sodium hydroxide
US6348128Mar 24, 1999Feb 19, 2002U.S. Borax Inc.Method of increasing the causticizing efficiency of alkaline pulping liquor by borate addition
US6635147 *May 14, 2000Oct 21, 2003U.S. Borax Inc.Quantitative analysis of sodium metaborates, carbonates, hydroxides and sulfides in basic wood pulping liquids by titration, colorimetric and/or spectrum analysis
US6663749Sep 25, 2001Dec 16, 2003U.S. Borax Inc.Sodium hydroxide is regenerated from sodium carbonate-containing smelts in pulp processes by autocauticization through the addition of limited amount of trisodium borate
US6913672 *Sep 11, 2003Jul 5, 2005U.S. Borax Inc.Quantitative, colorimetric analysis; calibration
US6946057 *Sep 12, 2003Sep 20, 2005Kiram AbAlkaline process for the manufacturing of pulp using alkali metaborate as buffering alkali
US7494637May 16, 2001Feb 24, 2009Massachusetts Institute Of TechnologyContinuously feeding into heated reaction chamber biomass material and exogenous metal oxide or its precursor, wherein the metal oxide is capable of forming a hydrolizable metal carbide, to form reaction products; quenching
CN101066516BJun 6, 2007Apr 20, 2011华东理工大学Decarbonizing solution comprising borate
EP0047656A1 *Sep 7, 1981Mar 17, 1982The Black Clawson CompanyProcess and apparatus for the oxygen delignification of pulp
EP1090181A1 *May 28, 1999Apr 11, 2001U.S. Borax Inc.Increasing causticizing efficiency of alkaline pulping liquor by borate addition
WO2001088257A1 *May 14, 2001Nov 22, 2001United States Borax IncMethods for analyzing boron-containing alkaline pulping liquors
WO2003062526A1 *Jan 22, 2003Jul 31, 2003Rinheat OyMethod for bleaching mechanically defibered pulp
WO2006019342A1 *Oct 1, 2004Feb 23, 2006Kiram AbPartial oxidation of cellulose spent pulping liquor
WO2011020949A1Aug 18, 2010Feb 24, 2011M-Real OyjMethod of producing sodium hydroxide from an effluent of fiber pulp production
Classifications
U.S. Classification162/32, 162/80, 162/65
International ClassificationD21C3/04, D21C9/10
Cooperative ClassificationD21C9/1068, D21C3/04
European ClassificationD21C3/04, D21C9/10J
Legal Events
DateCodeEventDescription
Jul 2, 1984ASAssignment
Owner name: A. AHLSTROM OSAKEYHTIO, SF-29600 NOORMARKKU, FINLA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:JANSON, JAN;REEL/FRAME:004275/0608
Effective date: 19840612